US5185033A - Gel-free paint containing copper pyrithione or pyrithione disulfide plus cuprous oxide - Google Patents

Gel-free paint containing copper pyrithione or pyrithione disulfide plus cuprous oxide Download PDF

Info

Publication number
US5185033A
US5185033A US07/938,962 US93896292A US5185033A US 5185033 A US5185033 A US 5185033A US 93896292 A US93896292 A US 93896292A US 5185033 A US5185033 A US 5185033A
Authority
US
United States
Prior art keywords
paint
pyrithione
cuprous oxide
disulfide
paint base
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US07/938,962
Inventor
Rahim Hani
Craig Waldron
Douglas A. Farmer, Jr.
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Olin Corp
Original Assignee
Olin Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=25472293&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=US5185033(A) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Priority to US07/938,962 priority Critical patent/US5185033A/en
Application filed by Olin Corp filed Critical Olin Corp
Assigned to OLIN CORPORATION, A CORP. OF VA reassignment OLIN CORPORATION, A CORP. OF VA ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: FARMER, DOUGLAS A., JR., HANI, RAHIM, WALDRON, CRAIG
Priority to US08/000,170 priority patent/US5252123A/en
Publication of US5185033A publication Critical patent/US5185033A/en
Application granted granted Critical
Priority to PCT/US1993/007749 priority patent/WO1994005736A1/en
Priority to JP6507224A priority patent/JP2942631B2/en
Priority to KR1019950700791A priority patent/KR100309753B1/en
Priority to EP93920151A priority patent/EP0658181B2/en
Priority to ES93920151T priority patent/ES2111771T5/en
Priority to HK98107152.2A priority patent/HK1008147B/en
Priority to DE69316761T priority patent/DE69316761T3/en
Priority to DK93920151.3T priority patent/DK0658181T4/en
Priority to AU50181/93A priority patent/AU5018193A/en
Priority to KR1019950702735A priority patent/KR100351015B1/en
Priority to NO950781A priority patent/NO309236B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
    • C09D5/1612—Non-macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides

Definitions

  • the present invention relates generally to paints and paint bases, and, more specifically to a process for providing a stable, gel-free di-spersion of copper pyrithione and pyrithione disulfide plus cuprous oxide biocide in paint.
  • Combinations of zinc pyrithione and cuprous oxide are known to be excellent antifouling agents when formulated into paints and paint bases (i.e., the paint before pigment addition) also containing rosin, as disclosed, for example, in U.S. Pat. No. 5,057,153.
  • paints and paint bases i.e., the paint before pigment addition
  • rosin rosin
  • the present invention provides one solution to this problem.
  • individually cuprous oxide, copper disulfide and copper pyrithione are all known biocides
  • the use of a combination of copper pyrithione or pyrithione di-sulfide plus cuprous oxide as biocides in the production of a paint which is stable against gellation during storage have not been known heretofore to the knowledge of the present inventors.
  • the present invention relates to a process for providing a gel-free paint or paint base characterized by biocidal efficacy.
  • the process comprises adding to a paint or paint base a biocidally effective amount of copper pyrithione or pyrithione disulfide plus cuprous oxide, or a combination thereof.
  • the present invention relates to a paint or paint base composition characterized by enhanced biocidal efficacy and gellation resistance wherein the paint or paint base contains a biocide consisting essentially of copper pyrithione or pyrithione disulfide and cuprous oxide, or a combination thereof.
  • the copper pyrithione or pyrithione disulfide, or combination thereof are present in an amount of between about 1% and about 25% (preferably 5-25%, more preferably 10-25%), and the cuprous oxide being present in an amount of between about 20% and about 70%, the total amount of said copper pyrithione or pyrithione disulfide plus said cuprous oxide being between about 20% and about 8%, based upon the total weight of the paint or paint base.
  • compositions of the present invention are storage stable and do not tend to form gels upon standing. This result is in distinct contrast to the tendency for zinc pyrithione plus cuprous oxide compositions to form gels, as illustrated by the specific examples provided hereinbelow.
  • the improved biocidal efficacy and gellation resistance advantages associated with the present invention are expected to provide advantages when used in a wide variety of paints, including indoor and outdoor household paints, industrial and commercial paints, particularly advantageous results are obtained when the process and composition of the present invention are utilized in conjunction with marine paints for use, for example, on ship's hulls.
  • the composition and process of the present invention provides highly desirable results in the context of exterior paints of both the latex and alkyd types.
  • a paint composition will contain a resin, an organic solvent (such as xylene or methylisobutylketone), a pigment, and various optional additives such as thickening agent(s), wetting agents, and the like, as is well-known in the art.
  • the resin is preferably selected from the group consisting of vinyl, alkyd, epoxy, acrylic, polyurethane and polyester resins, and combinations thereof.
  • the resin is preferably employed in an amount of between about 20% and about 80% based upon the weight of the paint or paint base.
  • the paint composition of the present invention optionally additionally contains optional additives which have a favorable influence on the viscosity, the wetting power and the dispersibility, as well as on the stability to freezing and electrolytes and on the foaming properties.
  • the total amount of optional additives is preferably no greater than 20% by weight, more preferably between about 1% and about 5% by weight, based upon the total weight of the paint composition.
  • Illustrative thickening agents include cellulose derivatives, for example methyl, hydroxyethyl, hydroxypropyl and carboxymethyl cellulose, poly(vinyl alcohol), poly (vinylpyrolidone), poly(ethylene-glycol), salts of poly(acrylic acid) and salts of acrylic acid/acrylamide copolymers.
  • Suitable wetting and dispersing agents include sodium polyphosphate, aryl or alkyl phosphates, salts of low-molecular-weight poly(acrylic acid), salts of poly(ethane-sulfonic acid), salts of poly (vinyl-phosphonic acid), salts of poly(maleic acid) and salts of copolymers of maleic acid with ethylene, 1-olefins with 3 to 18 carbon atoms and/or styrene.
  • ком ⁇ онент 1 for example glycol, propylene-glycol-(1,2), and butylene-glycol-(1,2) or polymers thereof, or ethoxylated compounds, for example reaction products of ethylene oxide with long-chain alkanols, amines, carboxylic acids, carboxylic acid amides, alkyd phenols, poly(propylene-glycol) or poly(butylene-glycol).
  • 1,2-diols for example glycol, propylene-glycol-(1,2), and butylene-glycol-(1,2) or polymers thereof
  • ethoxylated compounds for example reaction products of ethylene oxide with long-chain alkanols, amines, carboxylic acids, carboxylic acid amides, alkyd phenols, poly(propylene-glycol) or poly(butylene-glycol).
  • the minimum temperature of film formation (white point) of the paint composition may be reduced by adding solvents, such as ethylene-glycol, butyl-glycol, ethyl-glycol acetate, ethyl-diglycol acetate, butyl-diglycol acetate, benzene or alkylated aromatic hydrocarbosn.
  • solvents such as ethylene-glycol, butyl-glycol, ethyl-glycol acetate, ethyl-diglycol acetate, butyl-diglycol acetate, benzene or alkylated aromatic hydrocarbosn.
  • defoaming agents there are suitable for example poly(propylene-glycol) and polysiloxanes.
  • the paint composition of the present invention may be used as a paint for natural or synthetic materials for example wood, paper, metals, textiles and plastics. It is particularly suitable as an outdoor paint, and is excellent for use as a marine paint.
  • the paint preferably contains a swelling agent to cause the paint to gradually "slough off" in its marine environment, thereby causing renewed biocidal efficacy of newly exposed biocide (i.e., the copper pyrithione or pyrithione disulfide plus the cuprous oxide) at the surface of the paint nn contact with the water medium of the marine environment.
  • a swelling agent is naturally-occurring or synthetic clays, such as kaolin, montomorillonite (bentonite), clay mica (muscovite), and chlorite (hectonite), and the like.
  • swelling agents including natural or synthetic polymers, such as that commercially available as POLYMERGEL, have been found to be useful in the compositions of the present invention to provide the desired ablasive "sloughing off" effect.
  • Swelling agents can be used singly or in combination.
  • the total amount of optional additives is preferably no greater than 20% by weight, more preferably between about 1% and about 5% by weight, based upon the total weight of the paint composition.
  • a paint was prepared using the following formulation:
  • the solvent mixture used was a 1:2:1 mixture of xylene MIBK and carbitol acetate (called mixed solvent).
  • the zinc pyrithione used was standard commercial grade and assayed 97.8% pure by iodometric titration.
  • a one pint paint can was charged with 41.93 g of a 22.2% VAGH resin solution in a 2:1 mixture by volume of MIBK and xylene.
  • Tributyl phosphate was added to the paint can and mixed with a high speed disperser at 1000 RPM for 10 minutes.
  • the paint formulation made according to this procedure was of suitable viscosity for application by brush immediately after preparation, but thickened to an unportable paste after approximately 6 hours.
  • a paint was prepared using the following formulation:
  • the procedure was the same as the above example.
  • the formulation remained gel-free, and continues to remain gel-free, after seven months of storage .
  • a paint was prepared using the following formulation:
  • the procedure was the same as the above examples.
  • the paint remained gel-free and continues to remain gel-free after 10 weeks of storage.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Plant Pathology (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Paints Or Removers (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

The present invention relates generally to paints and paint bases, and, more specifically to a process for providing a stable gel-free dispersion of copper pyrithione or pyrithione disulfide plus cuprous oxide biocide in paint. The resulting paint is storage stable and remains gel-free after several months of storage at room temperature.

Description

FIELD OF THE INVENTION
The present invention relates generally to paints and paint bases, and, more specifically to a process for providing a stable, gel-free di-spersion of copper pyrithione and pyrithione disulfide plus cuprous oxide biocide in paint.
BACKGROUND OF THE INVENTION
Combinations of zinc pyrithione and cuprous oxide are known to be excellent antifouling agents when formulated into paints and paint bases (i.e., the paint before pigment addition) also containing rosin, as disclosed, for example, in U.S. Pat. No. 5,057,153. Unfortunately, however, such paints have now been found to thicken or gel unacceptably within a few days, at best, or a few hours, at worst, when formulated with typical commercial grades of zinc pyrithione in combination with cuprous oxide.
Heretofore, various solutions to the problem of gellation of paints containing rosin and zinc pyrithione in combination with cuprous oxide, have been suggested. Illustrative solutions have been to use rigorously purified zinc pyrithione, as disclosed in U.S. Pat. No. 5,098,473, or to add amines or esterified rosin, as disclosed in U.S. Pat. No. 5,112,397, or to use a metal salt of rosin, as disclosed in U.S. Pat. No. 5,137,569. Since these solutions may have drawbacks such as increased cost or lack of compatibility with some paints, a new, economical solution to the problem would be highly desired by the paint manufacturing community in order to maximize flexibility in using this combination of biocides in view of its excellent biocidal activity.
The present invention provides one solution to this problem. Although individually cuprous oxide, copper disulfide and copper pyrithione are all known biocides, the use of a combination of copper pyrithione or pyrithione di-sulfide plus cuprous oxide as biocides in the production of a paint which is stable against gellation during storage have not been known heretofore to the knowledge of the present inventors.
SUMMARY OF THE INVENTION
In one aspect, the present invention relates to a process for providing a gel-free paint or paint base characterized by biocidal efficacy. The process comprises adding to a paint or paint base a biocidally effective amount of copper pyrithione or pyrithione disulfide plus cuprous oxide, or a combination thereof.
In another aspect, the present invention relates to a paint or paint base composition characterized by enhanced biocidal efficacy and gellation resistance wherein the paint or paint base contains a biocide consisting essentially of copper pyrithione or pyrithione disulfide and cuprous oxide, or a combination thereof. Preferably, the copper pyrithione or pyrithione disulfide, or combination thereof, are present in an amount of between about 1% and about 25% (preferably 5-25%, more preferably 10-25%), and the cuprous oxide being present in an amount of between about 20% and about 70%, the total amount of said copper pyrithione or pyrithione disulfide plus said cuprous oxide being between about 20% and about 8%, based upon the total weight of the paint or paint base.
These and other aspects of the invention will become apparent upon reading the following detailed description of the invention.
DETAILED DESCRIPTION OF THE INVENTION
It has been surprisingly found that the compositions of the present invention are storage stable and do not tend to form gels upon standing. This result is in distinct contrast to the tendency for zinc pyrithione plus cuprous oxide compositions to form gels, as illustrated by the specific examples provided hereinbelow.
Although the improved biocidal efficacy and gellation resistance advantages associated with the present invention are expected to provide advantages when used in a wide variety of paints, including indoor and outdoor household paints, industrial and commercial paints, particularly advantageous results are obtained when the process and composition of the present invention are utilized in conjunction with marine paints for use, for example, on ship's hulls. In addition, the composition and process of the present invention provides highly desirable results in the context of exterior paints of both the latex and alkyd types.
Typically, a paint composition will contain a resin, an organic solvent (such as xylene or methylisobutylketone), a pigment, and various optional additives such as thickening agent(s), wetting agents, and the like, as is well-known in the art. The resin is preferably selected from the group consisting of vinyl, alkyd, epoxy, acrylic, polyurethane and polyester resins, and combinations thereof. The resin is preferably employed in an amount of between about 20% and about 80% based upon the weight of the paint or paint base.
In addition, the paint composition of the present invention optionally additionally contains optional additives which have a favorable influence on the viscosity, the wetting power and the dispersibility, as well as on the stability to freezing and electrolytes and on the foaming properties. The total amount of optional additives is preferably no greater than 20% by weight, more preferably between about 1% and about 5% by weight, based upon the total weight of the paint composition.
Illustrative thickening agents include cellulose derivatives, for example methyl, hydroxyethyl, hydroxypropyl and carboxymethyl cellulose, poly(vinyl alcohol), poly (vinylpyrolidone), poly(ethylene-glycol), salts of poly(acrylic acid) and salts of acrylic acid/acrylamide copolymers.
Suitable wetting and dispersing agents include sodium polyphosphate, aryl or alkyl phosphates, salts of low-molecular-weight poly(acrylic acid), salts of poly(ethane-sulfonic acid), salts of poly (vinyl-phosphonic acid), salts of poly(maleic acid) and salts of copolymers of maleic acid with ethylene, 1-olefins with 3 to 18 carbon atoms and/or styrene.
In order to increase the stability to freezing and electrolytes there may be added to the paint composition various monomer 1,2-diols, for example glycol, propylene-glycol-(1,2), and butylene-glycol-(1,2) or polymers thereof, or ethoxylated compounds, for example reaction products of ethylene oxide with long-chain alkanols, amines, carboxylic acids, carboxylic acid amides, alkyd phenols, poly(propylene-glycol) or poly(butylene-glycol).
The minimum temperature of film formation (white point) of the paint composition may be reduced by adding solvents, such as ethylene-glycol, butyl-glycol, ethyl-glycol acetate, ethyl-diglycol acetate, butyl-diglycol acetate, benzene or alkylated aromatic hydrocarbosn. As defoaming agents there are suitable for example poly(propylene-glycol) and polysiloxanes.
The paint composition of the present invention may be used as a paint for natural or synthetic materials for example wood, paper, metals, textiles and plastics. It is particularly suitable as an outdoor paint, and is excellent for use as a marine paint.
If a marine paint is being fabricated, the paint preferably contains a swelling agent to cause the paint to gradually "slough off" in its marine environment, thereby causing renewed biocidal efficacy of newly exposed biocide (i.e., the copper pyrithione or pyrithione disulfide plus the cuprous oxide) at the surface of the paint nn contact with the water medium of the marine environment. Illustrative swelling agents are naturally-occurring or synthetic clays, such as kaolin, montomorillonite (bentonite), clay mica (muscovite), and chlorite (hectonite), and the like. In addition to clays, other swelling agents, including natural or synthetic polymers, such as that commercially available as POLYMERGEL, have been found to be useful in the compositions of the present invention to provide the desired ablasive "sloughing off" effect. Swelling agents can be used singly or in combination. The total amount of optional additives is preferably no greater than 20% by weight, more preferably between about 1% and about 5% by weight, based upon the total weight of the paint composition.
The invention is further illustrated by the following Examples. Unless otherwise stated, the "parts" and "%" are "parts by weight" and "percent by weight", respectively based upon the weight of the paint or paint base.
While the invention has been described above with references to specific embodiments thereof, it is apparent that many changes, modifications and variations can be made without departing from the inventive concept disclosed herein. Accordingly, it is intended to embrace all such changes, modifications and variations that fall within the spirit and broad scope of the appended claims. All patent applications, patents and other publications cited herein are incorporated by reference in their entirety.
COMPARATIVE EXAMPLE A Demonstration of Gellation Results in a Paint containing Cuprous Oxide Plus Zinc Pyrithione
A paint was prepared using the following formulation:
The solvent mixture used was a 1:2:1 mixture of xylene MIBK and carbitol acetate (called mixed solvent).
The zinc pyrithione used was standard commercial grade and assayed 97.8% pure by iodometric titration.
______________________________________                                    
Material            Parts   %                                             
______________________________________                                    
VAGH resin (1)      9.3     2.8                                           
DISPERBYK 163 (2)   5.1     1.5                                           
Tributyl Phosphate  6.45    2.0                                           
Cuprous Oxide       136.5   41.4                                          
TITANOX (3)         7.5     2.3                                           
Zinc pyrithione powder                                                    
                    25.5    7.7                                           
Wood Rosin          6.3     1.9                                           
Solvent Mixture     133.0   40.0                                          
______________________________________                                    
 (1) vinyl chloridevinyl acetatevinyl alcohol terpolymer, a product of    
 Union Carbide Corporation.                                               
 (2) a high molecular weight block copolymer, a product of BYKChemie.     
 (3) titanium dioxide, a product of DuPont Company.
The procedure employed for preparing the paint was as follows:
(1) A one pint paint can was charged with 41.93 g of a 22.2% VAGH resin solution in a 2:1 mixture by volume of MIBK and xylene.
(2) A mixture of 5.1 g Disperbyk 163 an d5.1 g mixed solvent was added.
(3) Tributyl phosphate was added to the paint can and mixed with a high speed disperser at 1000 RPM for 10 minutes.
(4) The cuprous oxide, zinc pyrithione, titanox, and 10.8 g carbitol acetate were added to the paint can and mixing was continued at 7000 RPM for 1 hr.
(5) The mixing speed was reduced to 2500 RPM and 35 g of mixed solvent was added.
(6) Once the temperature dropped from 45° C. to below 35° C., a solution of 6.3 g of wood rosin in 50 g of mixed solvent was added to the can and the mixture was mixed for 1.0 hr. at 2500 RPM.
The paint formulation made according to this procedure was of suitable viscosity for application by brush immediately after preparation, but thickened to an unportable paste after approximately 6 hours.
EXAMPLE 1 Demonstration of Stable Paint Containing Cuprous Oxide and copper Pyrithione
A paint was prepared using the following formulation:
______________________________________                                    
Material           Parts   %                                              
______________________________________                                    
VAGH Resin         3.91    2.85                                           
Disperbyk 163      2.70    1.97                                           
Cuprous Oxide      75.0    54.82                                          
Copper Pyrithione  6.85    5.01                                           
Tricresyl Phosphate                                                       
                   3.6     2.63                                           
Wood Rosin WW      6.85    5.01                                           
Solvent Mixture    38.0    27.78                                          
______________________________________
The procedure was the same as the above example. The formulation remained gel-free, and continues to remain gel-free, after seven months of storage .
EXAMPLE 2 Stable Paint Containing Cuprous Oxide and Pyrithione Disulfide
A paint was prepared using the following formulation:
______________________________________                                    
Material           Parts   %                                              
______________________________________                                    
VAGH Resin         3.91    2.85                                           
Disperbyk 163      2.70    1.97                                           
Cuprous Oxide      75.0    54.82                                          
Pyrithione Disulfide                                                      
                   6.85    5.01                                           
Tricresyl Phosphate                                                       
                   3.6     2.63                                           
Wood Rosin WW      6.85    5.01                                           
Solvent Mixture    38.0    27.78                                          
______________________________________
The procedure was the same as the above examples. The paint remained gel-free and continues to remain gel-free after 10 weeks of storage.

Claims (10)

What is claimed is:
1. A paint or paint base composition characterized by enhanced biocidal efficacy and gellation resistance wherein the paint or paint base contains a biocide consisting essentially of cuprous oxide and copper pyrithione or pyrithione disulfide, or a combination thereof.
2. The paint or paint base of claim 1 wherein said copper pyrithione or pyrithione disulfide is present in an amount of between about 1% and about 25%, and said cuprous oxide being present in an amount of between about 20% and about 70%, the total amount of said copper pyrithione or pyrithione disulfide plus said cuprous oxide being between about 20% and about 80%, based upon the total weight of the paint or paint base.
3. The paint or paint base of claim 1 which additionally contains a resin selected from the group consisting of vinyl, alkyl, epoxy, acrylic, polyurethane and polyester resins, and combinations thereof.
4. The paint or paint base of claim 1 which additionally contains a swelling agent selected from the group consisting of natural and synthetic clay and natural and synthetic polymer swelling agents.
5. The paint or paint base of claim 4 wherein said swelling agent is selected from the group consisting of kaolin, montomorillonite (bentonite), clay mica (muscovite), and chlorite (hectonite), and combinations thereof.
6. A process for providing a gellation-inhibited paint or paint base containing copper pyrithione or pyrithione disulfide and cuprous oxide which comprises the step of adding said copper pyrithione or pyrithione disulfide and also adding cuprous oxide to a paint or paint base to provide a paint or paint base characterized by enhanced biocidal efficacy and resistance to gellation, said copper pyrithione or pyrithione disulfide being present in an amount of between about 1% and about 25%, and said cuprous oxide being present in an amount of between about 20% and about 70%, the total amount of said copper pyrithione or pyrithione disulfide plus said cuprous oxide being between about 20% and about 80% based upon the total weight of the paint or paint base.
7. The process of claim 6 wherein the total amount of copper pyrithione or pyrithione disulfide plus said cuprous oxide is between about 20% and about 75% based upon the total weight of the paint or paint base composition.
8. The process of claim 6 wherein said composition additionally contains a resin selected from the group consisting of vinyl, alkyl, epoxy, acrylic, polyurethane and polyester resins, and combinations thereof.
9. The process of claim 6 wherein said composition additionally contains a swelling agent selected from the group consisting of natural and synthetic clay and natural and synthetic polymer swelling agents.
10. The process of claim 9 wherein said swelling agent is selected from the group consisting of kaolin, montomorillonite (bentonite), clay mica (muscovite), and chlorite (hectonite), and combinations thereof.
US07/938,962 1992-09-01 1992-09-01 Gel-free paint containing copper pyrithione or pyrithione disulfide plus cuprous oxide Expired - Lifetime US5185033A (en)

Priority Applications (13)

Application Number Priority Date Filing Date Title
US07/938,962 US5185033A (en) 1992-09-01 1992-09-01 Gel-free paint containing copper pyrithione or pyrithione disulfide plus cuprous oxide
US08/000,170 US5252123A (en) 1992-09-01 1993-01-04 Gel-free paint containing cuprous oxide plus 2,2'-dithiobis (pyridine-1-oxide) compound
AU50181/93A AU5018193A (en) 1992-09-01 1993-08-18 Gel-free paint containing copper pyrithione
PCT/US1993/007749 WO1994005736A1 (en) 1992-09-01 1993-08-18 Gel-free paint containing copper pyrithione
DK93920151.3T DK0658181T4 (en) 1992-09-01 1993-08-18 Gel-free paint containing copper pyrithione
DE69316761T DE69316761T3 (en) 1992-09-01 1993-08-18 YELLOW COLOR CONTAINING COPPER PYRITHION
JP6507224A JP2942631B2 (en) 1992-09-01 1993-08-18 Non-gelling paint containing copper pyrithione
KR1019950700791A KR100309753B1 (en) 1992-09-01 1993-08-18 Ungelled paint composition containing copper pyrithione and preparation method thereof
EP93920151A EP0658181B2 (en) 1992-09-01 1993-08-18 Gel-free paint containing copper pyrithione
ES93920151T ES2111771T5 (en) 1992-09-01 1993-08-18 PAINT WITHOUT GELS CONTAINING COPPER PIRITION.
HK98107152.2A HK1008147B (en) 1992-09-01 1993-08-18 Gel-free paint containing copper pyrithione
KR1019950702735A KR100351015B1 (en) 1992-09-01 1993-12-17 Gel-resistant paint composition containing cuprous oxide and 2,2'-dithiobis (pyridine-1-oxide) compound and preparation method thereof
NO950781A NO309236B1 (en) 1992-09-01 1995-02-28 Gel-free paints containing copper pyritic and its process

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US07/938,962 US5185033A (en) 1992-09-01 1992-09-01 Gel-free paint containing copper pyrithione or pyrithione disulfide plus cuprous oxide

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US08/000,170 Continuation-In-Part US5252123A (en) 1992-09-01 1993-01-04 Gel-free paint containing cuprous oxide plus 2,2'-dithiobis (pyridine-1-oxide) compound

Publications (1)

Publication Number Publication Date
US5185033A true US5185033A (en) 1993-02-09

Family

ID=25472293

Family Applications (2)

Application Number Title Priority Date Filing Date
US07/938,962 Expired - Lifetime US5185033A (en) 1992-09-01 1992-09-01 Gel-free paint containing copper pyrithione or pyrithione disulfide plus cuprous oxide
US08/000,170 Expired - Lifetime US5252123A (en) 1992-09-01 1993-01-04 Gel-free paint containing cuprous oxide plus 2,2'-dithiobis (pyridine-1-oxide) compound

Family Applications After (1)

Application Number Title Priority Date Filing Date
US08/000,170 Expired - Lifetime US5252123A (en) 1992-09-01 1993-01-04 Gel-free paint containing cuprous oxide plus 2,2'-dithiobis (pyridine-1-oxide) compound

Country Status (10)

Country Link
US (2) US5185033A (en)
EP (1) EP0658181B2 (en)
JP (1) JP2942631B2 (en)
KR (2) KR100309753B1 (en)
AU (1) AU5018193A (en)
DE (1) DE69316761T3 (en)
DK (1) DK0658181T4 (en)
ES (1) ES2111771T5 (en)
NO (1) NO309236B1 (en)
WO (1) WO1994005736A1 (en)

Cited By (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5232493A (en) * 1992-09-01 1993-08-03 Olin Corporation Process for stabilizing zinc pyrithione plus cuprous oxide in paint
US5238490A (en) * 1992-09-04 1993-08-24 Olin Corporation Process for generating copper pyrithione in-situ in a paint formulation
US5252123A (en) * 1992-09-01 1993-10-12 Olin Corporation Gel-free paint containing cuprous oxide plus 2,2'-dithiobis (pyridine-1-oxide) compound
US5298061A (en) * 1993-05-14 1994-03-29 Olin Corporation Gel-free paint containing zinc pyrithione, cuprous oxide, and amine treated rosin
WO1994016024A1 (en) * 1993-01-04 1994-07-21 Olin Corporation Gel-free paint containing cuprous oxide plus 2,2'-dithiobis(pyridine-1-oxide) compound
US5342437A (en) * 1993-10-15 1994-08-30 Olin Corporation Gel-free paint containing zinc pyrithione cuprous oxide and carboxylic acid
GB2278361A (en) * 1993-05-26 1994-11-30 Waterline Paints Limited An anti-fouling paint
WO1995022905A1 (en) * 1994-02-28 1995-08-31 Olin Corporation Process for preparing copper pyrithione
US5518774A (en) * 1995-06-26 1996-05-21 Olin Corporation In-can and dry coating antimicrobial
US20020033114A1 (en) * 2000-01-26 2002-03-21 Asahi Glass Company, Limited Antifouling paint composition and product coated therewith
US6544440B1 (en) * 1999-03-17 2003-04-08 Api Corporation Coated bis(2-pyridinethiol-1-oxide) copper salt
WO2003028452A1 (en) * 2001-09-28 2003-04-10 Arch Chemicals, Inc. Non-dusting copper pyrithione dispersion
US6821326B2 (en) 2002-12-20 2004-11-23 Arch Chemicals, Inc. Small particle copper pyrithione
US20050118134A1 (en) * 2002-12-20 2005-06-02 Craig Waldron Small particle copper pyrithione
WO2005075582A1 (en) * 2004-02-03 2005-08-18 Akzo Nobel Coatings International B.V. Antifouling coating composition and its use on man made structures
US20050256235A1 (en) * 2004-05-11 2005-11-17 Kenneth Tseng Stabilized environmentally sensitive binders
US20070207178A1 (en) * 2006-03-03 2007-09-06 Craig Waldron Biocide composition comprising pyrithione and pyrrole derivatives
US20110206632A1 (en) * 2010-02-19 2011-08-25 Kappock Paul S Synthesis of zinc acrylate copolymer from acid functional copolymer, zinc pyrithione, and copper compound
US20120178847A1 (en) * 2009-07-16 2012-07-12 Bayer Materialscience Ag Polyurea-based fabric glue
WO2012150360A3 (en) * 2011-12-02 2013-03-07 Akzo Nobel Coatings International B.V. Waterborne antifouling coating composition
US9540520B2 (en) 2011-08-17 2017-01-10 Arch Chemicals, Inc. Synthesis of copper pyrithione from zinc pyrithione and copper compound
US9924715B2 (en) 2014-09-16 2018-03-27 Laboratoriya Bio Zet, Llc Zinc or copper (II) salt and use thereof as a biocide
US10442758B2 (en) 2013-10-08 2019-10-15 Laboratoriya Bio Zet, Llc Zinc or Copper (II) salt and use thereof as a biocide
US10721934B2 (en) 2013-11-19 2020-07-28 Arch Chemicals, Inc. Enhanced preservative
US11884841B2 (en) 2016-07-19 2024-01-30 Behr Process Corporation Antimicrobial paint composition and related methods
CN117645812A (en) * 2023-12-05 2024-03-05 广东嘉宝莉科技材料有限公司 Paint with high-performance broad-spectrum antibacterial and antiviral functions and application thereof

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5137569A (en) * 1991-10-10 1992-08-11 Olin Corporation Process for stabilizing zinc pyrithione plus cuprous oxide in paint
IL123895A (en) * 1997-04-14 2003-04-10 Rohm & Haas Pesticide compositions and method for controlling pests using such compositions

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3615744A (en) * 1967-07-03 1971-10-26 Takeda Chemical Industries Ltd Antifouling paints
US4039312A (en) * 1972-07-04 1977-08-02 Marcel Joseph Gaston Patru Bacteriostatic, fungistatic and algicidal compositions, particularly for submarine paints
EP0108634A1 (en) * 1982-11-08 1984-05-16 INTERNATIONAL PAINT Public Limited Company Marine antifouling paint
US4581351A (en) * 1982-11-23 1986-04-08 Sutton Laboratories, Inc. Composition of matter containing imidazolidinyl urea and pyrithione and its derivatives
US4918147A (en) * 1986-11-17 1990-04-17 Nippon Paint Co., Ltd. Preparation of metal containing resin composition and antifouling paint containing said composition
WO1991014743A1 (en) * 1990-03-21 1991-10-03 Courtaulds Coatings (Holdings) Limited Antifouling coating compositions
US5057153A (en) * 1990-05-03 1991-10-15 Olin Corporation Paint containing high levels of a pyrithione salt plus a copper salt
US5098473A (en) * 1991-03-04 1992-03-24 Olin Corporation Process for stabilizing zinc pyrithione plus cuprous oxide in paint
US5112397A (en) * 1991-06-17 1992-05-12 Olin Corporation Process for stabilizing zinc pyrithione plus cuprous oxide in paint
US5137569A (en) * 1991-10-10 1992-08-11 Olin Corporation Process for stabilizing zinc pyrithione plus cuprous oxide in paint

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2696188B2 (en) * 1992-07-08 1998-01-14 大日本製薬株式会社 Antifouling paint composition
US5185033A (en) * 1992-09-01 1993-02-09 Olin Corporation Gel-free paint containing copper pyrithione or pyrithione disulfide plus cuprous oxide

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3615744A (en) * 1967-07-03 1971-10-26 Takeda Chemical Industries Ltd Antifouling paints
US4039312A (en) * 1972-07-04 1977-08-02 Marcel Joseph Gaston Patru Bacteriostatic, fungistatic and algicidal compositions, particularly for submarine paints
EP0108634A1 (en) * 1982-11-08 1984-05-16 INTERNATIONAL PAINT Public Limited Company Marine antifouling paint
US4581351A (en) * 1982-11-23 1986-04-08 Sutton Laboratories, Inc. Composition of matter containing imidazolidinyl urea and pyrithione and its derivatives
US4918147A (en) * 1986-11-17 1990-04-17 Nippon Paint Co., Ltd. Preparation of metal containing resin composition and antifouling paint containing said composition
WO1991014743A1 (en) * 1990-03-21 1991-10-03 Courtaulds Coatings (Holdings) Limited Antifouling coating compositions
US5057153A (en) * 1990-05-03 1991-10-15 Olin Corporation Paint containing high levels of a pyrithione salt plus a copper salt
US5098473A (en) * 1991-03-04 1992-03-24 Olin Corporation Process for stabilizing zinc pyrithione plus cuprous oxide in paint
US5112397A (en) * 1991-06-17 1992-05-12 Olin Corporation Process for stabilizing zinc pyrithione plus cuprous oxide in paint
US5137569A (en) * 1991-10-10 1992-08-11 Olin Corporation Process for stabilizing zinc pyrithione plus cuprous oxide in paint

Cited By (54)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5252123A (en) * 1992-09-01 1993-10-12 Olin Corporation Gel-free paint containing cuprous oxide plus 2,2'-dithiobis (pyridine-1-oxide) compound
US5232493A (en) * 1992-09-01 1993-08-03 Olin Corporation Process for stabilizing zinc pyrithione plus cuprous oxide in paint
US5238490A (en) * 1992-09-04 1993-08-24 Olin Corporation Process for generating copper pyrithione in-situ in a paint formulation
WO1994016024A1 (en) * 1993-01-04 1994-07-21 Olin Corporation Gel-free paint containing cuprous oxide plus 2,2'-dithiobis(pyridine-1-oxide) compound
WO1994026826A1 (en) * 1993-05-14 1994-11-24 Olin Corporation Paint containing zinc pyrithione, cuprous oxide and rosin
CN1051332C (en) * 1993-05-14 2000-04-12 阿奇化工公司 Paint and base compositions containing zinc pyrithione, cuprous oxide, and rosin, and methods of forming the same
US5298061A (en) * 1993-05-14 1994-03-29 Olin Corporation Gel-free paint containing zinc pyrithione, cuprous oxide, and amine treated rosin
GB2278361A (en) * 1993-05-26 1994-11-30 Waterline Paints Limited An anti-fouling paint
US5342437A (en) * 1993-10-15 1994-08-30 Olin Corporation Gel-free paint containing zinc pyrithione cuprous oxide and carboxylic acid
WO1995010568A1 (en) * 1993-10-15 1995-04-20 Olin Corporation Gel-free paint containing zinc pyrithione
WO1995022905A1 (en) * 1994-02-28 1995-08-31 Olin Corporation Process for preparing copper pyrithione
JP3062825B2 (en) 1994-02-28 2000-07-12 オリン コーポレイション Method for producing copper pyrithione
US5540860A (en) * 1994-02-28 1996-07-30 Olin Corporation Process for preparing copper pyrithione
US5650095A (en) * 1994-02-28 1997-07-22 Olin Corporation Process for preparing copper pyrithione
WO1997001397A1 (en) * 1995-06-26 1997-01-16 Olin Corporation In-can and dry coating antimicrobial
US5518774A (en) * 1995-06-26 1996-05-21 Olin Corporation In-can and dry coating antimicrobial
US6544440B1 (en) * 1999-03-17 2003-04-08 Api Corporation Coated bis(2-pyridinethiol-1-oxide) copper salt
US6630079B2 (en) 1999-03-17 2003-10-07 Api Corporation Coated bis (2-pyridinethiol-1-oxide) copper salt
US20020033114A1 (en) * 2000-01-26 2002-03-21 Asahi Glass Company, Limited Antifouling paint composition and product coated therewith
WO2003028452A1 (en) * 2001-09-28 2003-04-10 Arch Chemicals, Inc. Non-dusting copper pyrithione dispersion
US6627665B2 (en) * 2001-09-28 2003-09-30 Arch Chemicals, Inc. Non-dusting copper pyrithione dispersion
US6821326B2 (en) 2002-12-20 2004-11-23 Arch Chemicals, Inc. Small particle copper pyrithione
US20050118134A1 (en) * 2002-12-20 2005-06-02 Craig Waldron Small particle copper pyrithione
US7481873B2 (en) 2002-12-20 2009-01-27 Arch Chemicals, Inc. Small particle copper pyrithione
US20080124298A1 (en) * 2004-02-03 2008-05-29 Akzo Nobel Coating International B.V. Antifouling Coating Composition and Its Use on Man Made Structures
AU2005211460B2 (en) * 2004-02-03 2010-09-23 Akzo Nobel Coatings International B.V. Antifouling coating composition and its use on man made structures
WO2005075582A1 (en) * 2004-02-03 2005-08-18 Akzo Nobel Coatings International B.V. Antifouling coating composition and its use on man made structures
CN100551977C (en) * 2004-02-03 2009-10-21 阿克佐诺贝尔涂层国际有限公司 Antifouling coating composition and its use on man-made structures
US20050256235A1 (en) * 2004-05-11 2005-11-17 Kenneth Tseng Stabilized environmentally sensitive binders
US20110143153A1 (en) * 2006-03-03 2011-06-16 Craig Waldron Biocide composition comprising pyrithione and pyrrole derivatives
US7893047B2 (en) 2006-03-03 2011-02-22 Arch Chemicals, Inc. Biocide composition comprising pyrithione and pyrrole derivatives
US20110104375A1 (en) * 2006-03-03 2011-05-05 Craig Waldron Biocide composition comprising pyrithione and pyrrole derivatives
US20110144232A1 (en) * 2006-03-03 2011-06-16 Craig Waldron Biocide composition comprising pyrithione and pyrrole derivatives
EP3231283A1 (en) 2006-03-03 2017-10-18 Arch Chemicals, Inc. Biocide composition comprising zinc pyrithione and a pyrrole derivative
US8372829B2 (en) 2006-03-03 2013-02-12 Arch Chemicals, Inc. Biocide composition comprising pyrithione and pyrrole derivatives
US8481523B2 (en) 2006-03-03 2013-07-09 Arch Chemicals, Inc. Biocide composition comprising pyrithione and pyrrole derivatives
US20070207178A1 (en) * 2006-03-03 2007-09-06 Craig Waldron Biocide composition comprising pyrithione and pyrrole derivatives
US9051410B2 (en) * 2009-07-16 2015-06-09 Medical Adhesive Revolution Gmbh Polyurea-based fabric glue
US20120178847A1 (en) * 2009-07-16 2012-07-12 Bayer Materialscience Ag Polyurea-based fabric glue
US9717819B2 (en) 2009-07-16 2017-08-01 Adhesys Medical Gmbh Polyurea-based fabric glue
US9404026B2 (en) 2009-07-16 2016-08-02 Adhesys Medical Gmbh Polyurea-based fabric glue
US20130183362A1 (en) * 2010-02-19 2013-07-18 Arch Chemicals, Inc. Synthesis of zinc acrylate copolymer from acid functional copolymer, zinc pyrithione, and copper compound
US9156997B2 (en) * 2010-02-19 2015-10-13 Arch Chemicals, Inc. Synthesis of zinc acrylate copolymer from acid functional copolymer, zinc pyrithione, and copper compound
US8541493B2 (en) * 2010-02-19 2013-09-24 Arch Chemicals, Inc. Synthesis of zinc acrylate copolymer from acid functional copolymer, zinc pyrithione, and copper compound
US20110206632A1 (en) * 2010-02-19 2011-08-25 Kappock Paul S Synthesis of zinc acrylate copolymer from acid functional copolymer, zinc pyrithione, and copper compound
US9540520B2 (en) 2011-08-17 2017-01-10 Arch Chemicals, Inc. Synthesis of copper pyrithione from zinc pyrithione and copper compound
US9290669B2 (en) 2011-12-02 2016-03-22 Akzo Nobel Coatings International B.V. Waterborne antifouling coating composition
AU2012251537B2 (en) * 2011-12-02 2016-08-18 Akzo Nobel Coatings International B.V. Waterborne antifouling coating composition
WO2012150360A3 (en) * 2011-12-02 2013-03-07 Akzo Nobel Coatings International B.V. Waterborne antifouling coating composition
US10442758B2 (en) 2013-10-08 2019-10-15 Laboratoriya Bio Zet, Llc Zinc or Copper (II) salt and use thereof as a biocide
US10721934B2 (en) 2013-11-19 2020-07-28 Arch Chemicals, Inc. Enhanced preservative
US9924715B2 (en) 2014-09-16 2018-03-27 Laboratoriya Bio Zet, Llc Zinc or copper (II) salt and use thereof as a biocide
US11884841B2 (en) 2016-07-19 2024-01-30 Behr Process Corporation Antimicrobial paint composition and related methods
CN117645812A (en) * 2023-12-05 2024-03-05 广东嘉宝莉科技材料有限公司 Paint with high-performance broad-spectrum antibacterial and antiviral functions and application thereof

Also Published As

Publication number Publication date
KR950703032A (en) 1995-08-23
ES2111771T3 (en) 1998-03-16
DK0658181T3 (en) 1998-09-23
US5252123A (en) 1993-10-12
HK1008147A1 (en) 1999-04-30
EP0658181B2 (en) 2008-01-23
EP0658181A4 (en) 1996-02-21
NO950781D0 (en) 1995-02-28
DK0658181T4 (en) 2010-01-25
NO950781L (en) 1995-02-28
KR960700314A (en) 1996-01-19
NO309236B1 (en) 2001-01-02
EP0658181A1 (en) 1995-06-21
DE69316761D1 (en) 1998-03-05
JP2942631B2 (en) 1999-08-30
DE69316761T2 (en) 1998-08-06
EP0658181B1 (en) 1998-01-28
AU5018193A (en) 1994-03-29
JPH08501121A (en) 1996-02-06
DE69316761T3 (en) 2008-08-28
KR100309753B1 (en) 2001-12-28
KR100351015B1 (en) 2003-09-19
WO1994005736A1 (en) 1994-03-17
ES2111771T5 (en) 2008-06-16

Similar Documents

Publication Publication Date Title
US5185033A (en) Gel-free paint containing copper pyrithione or pyrithione disulfide plus cuprous oxide
US5137569A (en) Process for stabilizing zinc pyrithione plus cuprous oxide in paint
US5246489A (en) Process for generating copper pyrithione in-situ in a paint formulation
US5098473A (en) Process for stabilizing zinc pyrithione plus cuprous oxide in paint
US5342437A (en) Gel-free paint containing zinc pyrithione cuprous oxide and carboxylic acid
US5112397A (en) Process for stabilizing zinc pyrithione plus cuprous oxide in paint
US5298061A (en) Gel-free paint containing zinc pyrithione, cuprous oxide, and amine treated rosin
HK1008039B (en) Process for stabilizing paint
US5238490A (en) Process for generating copper pyrithione in-situ in a paint formulation
US5232493A (en) Process for stabilizing zinc pyrithione plus cuprous oxide in paint
EP0677088B1 (en) Gel-free paint containing cuprous oxide plus 2,2'-dithiobis(pyridine-1-oxide) compound
HK1008147B (en) Gel-free paint containing copper pyrithione
WO1992015647A1 (en) Process for stabilizing zinc pyrithione plus cuprous oxide in paint

Legal Events

Date Code Title Description
AS Assignment

Owner name: OLIN CORPORATION, A CORP. OF VA, CONNECTICUT

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:HANI, RAHIM;WALDRON, CRAIG;FARMER, DOUGLAS A., JR.;REEL/FRAME:006249/0183

Effective date: 19920901

FEPP Fee payment procedure

Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

STCF Information on status: patent grant

Free format text: PATENTED CASE

FPAY Fee payment

Year of fee payment: 4

FEPP Fee payment procedure

Free format text: PAYER NUMBER DE-ASSIGNED (ORIGINAL EVENT CODE: RMPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

FPAY Fee payment

Year of fee payment: 8

FPAY Fee payment

Year of fee payment: 12